Pigments Containing Particles Mainly Composed of Perovskite Composite Oxides and Their Use

Abstract

A pigment having a lattice constant a of more than and less than the above, and containing particles mainly composed of a perovskite composite oxide. This pigment selectively transmits light in the warm color region and can be used as a substitute material for titanium oxide. This pigment can be used for, for example, cosmetic applications.

Description

Technical Field

[0001] The present invention relates to a pigment containing particles mainly composed of a perovskite composite oxide, and particularly to the above-mentioned pigment having a warm-color light transmission effect. Background Art

[0002] Conventionally, for makeup cosmetics such as foundation, in order to cover red blood streaks, dullness, wrinkles, freckles, etc. caused by the skin and present a skin with a uniform and beautiful appearance, it has been used as a cosmetic for changing the skin tone by adding a titanium oxide pigment with strong coloring power and other colorants such as inorganic pigments and organic pigments.

[0003] For the aforementioned titanium oxide, in order to make the skin tone uniform, a pigment with strong coloring power and covering power is usually used. For titanium oxide, a pigment-grade titanium oxide having a rutile crystal form and a primary particle size of 0.1 μm or more and 0.3 μm or less is widely used. However, when the skin is made up with a foundation containing this titanium oxide, the intensity of white scattered light becomes too strong, and sometimes the makeup surface of the makeup appears pale and unnatural, and there is a problem of so-called floating powder phenomenon.

[0004] As one of the means to prevent the floating powder phenomenon, it is possible to obtain a balance between coloring power, covering power, and the intensity of white scattered light by using rutile-type titanium oxide having a specific shape. For example, Japanese Patent No. 4684970 (Patent Document 1) describes a cosmetic containing an aggregate of fan-shaped rutile-type titanium oxide particles formed by aggregating and / or bonding rod-shaped primary particles. In addition, Japanese Patent No. 6258462 (Patent Document 2) describes a rutile-type titanium dioxide powder obtained by calcining rutile-type titanium dioxide having needle-like protrusions on the particle surface and mixing it into a cosmetic.

[0005] As another means to prevent the floating powder phenomenon, a method of utilizing the scattering of light in the warm-color region inside the skin can be cited. Japanese Patent No. 5363696 (Patent Document 3) focused on the light transmitted into the skin under natural conditions and conducted research. Specifically, it is described that in a light-scattering medium such as the skin, a part of the light irradiated on the skin is transmitted inward and reflected by internal scatterers, and thus it is also emitted from a part different from the irradiation site. However, by using a coloring material having a small light absorption rate at a wavelength of 630 nm to 700 nm for skin cosmetics, the distribution of the above-mentioned emission sites is close to that under natural conditions, and a natural texture can be obtained.

[0006] However, in recent years, with regard to titanium(IV) oxide containing rutile-type titanium oxide, the possibility of harming health cannot be denied. Therefore, mainly in Europe, there is a tendency to reduce the usage amount or use substitute materials. In Japanese Patent Laid-Open No. 5-339121 (Document 4), as pigments other than rutile-type titanium oxide, compounds having a perovskite-type crystal structure such as calcium titanate, strontium titanate, barium titanate, calcium zirconate, and strontium zirconate are proposed. Japanese Patent No. 3464564 (Patent Document 5) describes a UV-protective cosmetic using particles of a composite oxide having a perovskite-type structure or a solid solution thereof.

[0007] Prior Art Documents

[0008] Patent Documents

[0009] Patent Document 1: Japanese Patent No. 4684970

[0010] Patent Document 2: Japanese Patent No. 6258462

[0011] Patent Document 3: Japanese Patent No. 5363696

[0012] Patent Document 4: Japanese Patent Laid-Open No. 5-339121

[0013] Patent Document 5: Japanese Patent No. 3464564 Summary of the Invention

[0014] Problems to be Solved by the Invention

[0015] However, in Patent Document 4, only lubricity, adhesiveness, and covering power are discussed, and no countermeasures against powder floating phenomenon are considered. In addition, Patent Document 4 only describes that a powder containing particles formed of a compound having a perovskite-type crystal structure, having an average particle size in the range of 0.05 to 15 μm, and having an equiaxed shape is compounded in a cosmetic, but does not describe a specific production method of such a powder. In addition, in Patent Document 5, although the synthesis of a composite oxide powder represented by CaTiO 3 is described, no specific example of a cosmetic compounded with this powder is described; in addition, although the UV protection effect, safety, and stability of a cosmetic containing a composite oxide having a perovskite-type crystal structure are described, no research on countermeasures against powder floating phenomenon is conducted.

[0016] Although the development of substitute materials for titanium oxide is underway, the development of cosmetics that achieve a natural makeup look is still in progress. In particular, a substitute material for titanium oxide that can obtain the effect of selectively transmitting light in the warm color region cannot be obtained.

[0017] An object of the present invention is to provide a pigment that selectively transmits light in the warm color region and can be used as a substitute material for titanium oxide.

[0018] Solutions for Solving the Problems

[0019] The inventors of the present invention focused on perovskite composite oxides as a substitute material for titanium oxide and conducted in-depth research. As a result, it was found that a pigment containing particles mainly composed of a perovskite composite oxide with a specific crystal structure selectively transmits light in the warm color region.

[0020] The present invention is not limited to these, but includes the following.

[0021] [1] A pigment having a lattice constant a of or more and or less, and containing particles mainly composed of a perovskite composite oxide.

[0022] [2] The pigment according to [1], wherein the perovskite composite oxide is an orthorhombic perovskite composite oxide.

[0023] [3] The pigment according to [1] or [2], wherein in X-ray diffraction measurement, when the height of the diffraction line of the (121) plane appearing in the range of diffraction angle of 32.50° or more and 33.50° or less is set to 100.0, the height of the diffraction line of the (202) plane appearing in the range of diffraction angle of 46.75° or more and 47.75° or less is 50.0 or less.

[0024] [4] The pigment according to any one of [1] to [3], having a specific surface area of 3.0 m 2 / g or more.

[0025] [5] The pigment according to any one of [1] to [4], wherein in X-ray diffraction measurement, when the integrated diffraction intensity of the (121) plane appearing in the range of diffraction angle of 32.50° or more and 33.50° or less is set to 100.0, no diffraction line having an integrated diffraction intensity greater than 12.00 appears in the range of diffraction angle of 24.75° or more and 28.00° or less.

[0026] [6] The pigment according to any one of [1] to [5], wherein at least a part of the surface of the particles has a covering layer of an inorganic substance and / or an organic substance.

[0027] [7] The pigment according to any one of [1] to [6], wherein the particle shape is substantially spherical.

[0028] [8] The pigment according to any one of [1] to [6], wherein the particle shape is rectangular parallelepiped.

[0029] [9] The pigment according to any one of [1] to [8], wherein the microcrystalline diameter of the particles is above and below.

[0030]

[10] A cosmetic comprising the pigment according to any one of [1] to [9].

[0031]

[11] A film composition comprising the pigment according to any one of [1] to [9].

[0032]

[12] A resin composition comprising the pigment according to any one of [1] to [9].

[0033]

[13] A coating material comprising the pigment according to any one of [1] to [9].

[0034]

[14] An ink comprising the pigment according to any one of [1] to [9].

[0035] Effects of the Invention

[0036] The pigment obtained by the present invention, which contains particles mainly composed of a perovskite composite oxide, can selectively transmit light in the warm color region.

[0037] The pigment obtained by the present invention, especially when used as a material for cosmetics such as foundation applied to the skin, the light in the warm color region transmitted will scatter inside the skin, thereby enabling a natural makeup look.

[0038] In addition, the pigment obtained by the present invention can also be used as a substitute material for titanium oxide. The perovskite composite oxide used in the pigment of the present invention has the same ultraviolet ray shielding effect as titanium oxide, and thus can be used in sunscreen products, etc.

[0039] The pigment obtained by the present invention can, in fields other than cosmetics, exhibit the function of transmitting light in the warm color region and be used for various purposes. As such uses, for example, but not limited to these, it can be mentioned that it is added to a transparent material and used for components of optical instruments, added to a resin to form a resin composition having a warm color light transmission effect, added to a coating material and used for residential coatings, etc. BRIEF DESCRIPTION OF THE DRAWINGS

[0040] Figure 1 The X-ray diffraction pattern of the perovskite composite oxide shown by the chemical formula CaTiO 3 for PDF card registration.

[0041] Figure 2 The X-ray diffraction pattern of the pigment formed from particles mainly composed of a perovskite composite oxide obtained in Example 4.

[0042] Figure 3 Registered for PDF card, chemical formula CaTiO 3 Among the X-ray diffraction patterns of the perovskite composite oxide shown, the part where the diffraction angle 2θ is 45.0° or more and 50.0° or less.

[0043] Figure 4 Among the X-ray diffraction patterns of the pigment obtained in Example 4, the part where the diffraction angle 2θ is 45.0° or more and 50.0° or less.

[0044] Figure 5 Transmission electron micrograph of the pigment obtained in Example 4.

[0045] Figure 6 Transmission electron micrograph of the pigment obtained in Example 1. Detailed Description

[0046] The present invention relates to a pigment formed of particles mainly composed of a perovskite composite oxide having a lattice constant a of or more and or less.

[0047] The meaning of "a pigment formed of particles mainly composed of a perovskite composite oxide" is that each particle constituting the pigment is mainly a particle of a perovskite composite oxide. Specifically, it means that 850 g / kg or more, preferably 900 g / kg or more, of each particle constituting the pigment is a particle of a perovskite composite oxide. Among the particles constituting the pigment of the present invention, in addition to the perovskite composite oxide, unreacted substances during the synthesis reaction of the perovskite composite oxide, inevitable impurities derived from raw materials, and inorganic and / or organic substances derived from the coating layer may be included.

[0048] The perovskite composite oxide as the main component of the particles constituting the pigment of the present invention is preferably an orthorhombic perovskite composite oxide. "Orthorhombic perovskite composite oxide" refers to a perovskite composite oxide in which the angles between two different crystal axes are both 90°.

[0049] For a pigment containing particles mainly composed of the perovskite composite oxide of the present invention, when the space group of the perovskite crystal structure is Pnma(62), compared with the normal perovskite composite oxide shown by the chemical formula CaTiO 3 it is characterized in that the lattice constant a is large. When the lattice constant a is large, the reason for selectively transmitting light in the warm color region is not clear, but the reason is considered as follows. When the lattice constant a becomes larger, the arrangement of the crystals becomes disordered, and in particular, light in the low wavelength region is easily attenuated. As a result, it becomes selective to transmit light in the long wavelength region (i.e., light in the warm color region). The lattice constant a is preferably or more. More preferably Above, more preferably Above. On the other hand, when the lattice constant a further increases, the lattice constant b approaches the value of the lattice constant a, and the regularity of the recrystallization filling improves, so the function of selectively transmitting light in the warm color region is lost. The lattice constant a is preferably Below, more preferably Below, even more preferably Below.

[0050] In addition, in the pigment of the present invention, compared with the normal perovskite composite oxide shown by the chemical formula CaTiO 3 When the lattice constant a increases compared with the normal perovskite composite oxide shown, the positions of the diffraction lines of each crystal plane measured by X-ray diffraction based on the powder method will change. Specifically, the diffraction line from the crystal plane with Miller index (202) moves to the low-angle side. On the other hand, the diffraction line from the crystal plane with Miller index (040) does not move. As a result, in the range where the diffraction angle 2θ is 46.75° or more and 47.75° or less, the diffraction lines of the (202) plane and the (040) plane observed overlapping at the same position are clearly separated, and the height of the highest part of the diffraction line becomes smaller compared with before separation. Specifically, in the present invention, when the height of the diffraction line of the (121) plane appears in the range where the diffraction angle 2θ of the largest diffraction line of the perovskite composite oxide is 32.50° or more and 33.50° or less is 100.0, the height of the diffraction line of the (202) plane (hereinafter referred to as "XRD diffraction line height ratio") is preferably 50.0 or less. More preferably 48.0 or less, even more preferably 46.0 or less.

[0051] The pigment of the present invention preferably has a large specific surface area. The reason is not clear yet, but it can be considered as follows. There are irregularities and cracks on the surface of the particles mainly composed of the perovskite composite oxide used in the present invention. Light with a short wavelength is easily scattered by these irregularities and cracks, while light in the warm color region with a long wavelength is not greatly affected. Therefore, the more irregularities and cracks on the particles, the easier it is to selectively transmit light in the warm color region. The specific surface area is preferably 3.0 m 2 / g or more, more preferably 3.5 m 2 / g or more. There is no particular upper limit for the specific surface area of the pigment of the present invention. When it is 200 m 2 / g or less, from the viewpoint that the oil absorption amount will not become too large, advantages such as being able to easily control the properties of cosmetics can be obtained, so it is preferred.

[0052] Pigments containing particles mainly composed of the perovskite composite oxide of the present invention can be used as a substitute material for cosmetics using titanium oxide, and thus a small content of titanium oxide is desired. To calculate the exact content of titanium oxide in the perovskite composite oxide, it is necessary to mix the perovskite composite oxide of the present invention and titanium oxide and perform X-ray diffraction measurement based on the powder method. A standard curve needs to be made, and this method requires a lot of time and cost. Therefore, as a method for more simply confirming that the content of titanium oxide is small, in the X-ray diffraction measurement based on the powder method, the integrated diffraction intensity ratio of the diffraction line of the (121) plane that appears above 32.50° and below 33.50° with the strongest integrated diffraction intensity in the perovskite composite oxide is compared with the integrated diffraction intensity of the diffraction line that appears above 24.75° and below 28.00° in rutile-type, anatase-type, and brookite-type titanium oxides. From the viewpoint of a small content of titanium oxide, in the present invention, when the integrated diffraction intensity of the diffraction line of the (121) plane that appears above 32.50° and below 33.50° is 100.0, in the range above 24.75° and below 28.00°, it is preferably that no diffraction line with an integrated diffraction intensity greater than 12.00 appears. When the integrated diffraction intensity of the diffraction line of the (121) plane that appears above 32.50° and below 33.50° is 100.0, the integrated diffraction intensity ratio of the diffraction line that appears above 24.75° and below 28.00° (hereinafter referred to as the "XRD titanium oxide integrated diffraction intensity") is further preferably 11.00 or less, and more preferably 8.50 or less. It should be noted that there is a diffraction line of the (111) plane of the perovskite composite oxide above 24.75° and below 28.00°. When the integrated intensity of the diffraction line of the (121) plane is 100.0, the integrated diffraction intensity of this (111) plane diffraction line is about 3. Therefore, even when completely free of titanium oxide, the above integrated diffraction intensity will not be zero.

[0053] The pigments obtained in the present invention have a substantially spherical particle shape and a cuboid shape. "Substantially spherical" means that, as shown in Figure 5 , the primary particles or secondary particles crystallize and grow isotropically, or form an aggregate isotropically, having an irregular shape or an approximately spherical outer shape, and a circularity of 0.790 or more calculated by the method described below. For example, shapes such as the cuboid shape shown in Figure 6 , or the elongated needle shape, or a shape similar to a sea urchin with protrusions having a length equal to or greater than the diameter of the central part do not belong to "substantially spherical". "Cuboid shape" means that, as shown in Figure 6As shown, compared with the other two axes, primary particles or secondary particles have more crystal growth in a specific one-axis direction or form more aggregates in a specific one-axis direction, thus having an approximate cuboid shape, and those with a circularity less than 0.790 calculated by the method described below. When called "cuboid-shaped", it does not need to be a complete cuboid (all six faces are formed into rectangles or squares). In addition, the shape of the particle cross-section perpendicular to the long axis direction does not need to be a rectangle or square, and the cross-section shapes of all cross-sections do not need to be the same shape.

[0054] "The particle shape is approximately spherical" or "the particle shape is large cuboid-shaped" includes cases where 80% or more, preferably 85% or more by number of the particles constituting the pigment of the present invention are approximately spherical or cuboid-shaped respectively.

[0055] The perovskite composite oxide, which is the main component of the particles constituting the pigment of the present invention, usually has a tendency of insufficient crystal growth and unstable properties when the microcrystal diameter is small. Therefore, the microcrystal diameter of the particles constituting the pigment based on X-ray diffraction is preferably above, and more preferably greater than From the viewpoint of the touch when used in cosmetics, the upper limit of the microcrystal diameter is preferably below. The microcrystal diameter can be measured by the method described below.

[0056] The pigment of the present invention preferably has a small particle size distribution. When the particle size distribution is large, the particles become uneven, and there is a tendency for the lubricity to deteriorate when used in cosmetics. From the viewpoint of the lubricity when used in cosmetics, the particle size distribution calculated by the method described below is preferably 10.00 or less, more preferably 8.00 or less, and still more preferably 5.00 or less.

[0057] The pigment of the present invention preferably has good lubricity. The lubricity of a pigment with a small particle size distribution tends to be good. In addition, generally, if the particles are cuboid-shaped and approximately spherical, the lubricity of the approximately spherical particles tends to be good. Therefore, from the viewpoint of lubricity, it is preferable that the circularity of the particles is large.

[0058] The warm-color light transmission effect of the pigment of the present invention calculated by the method described below is preferably 0.56 or more. When the warm-color light transmission effect is 0.56 or more, when used in cosmetics, the reflection in the warm-color region inside the skin becomes sufficient, and a natural makeup is obtained. It should be noted that the upper limit value of the warm-color light transmission effect is not particularly limited, but the theoretical maximum value of the warm-color light transmission effect calculated by the evaluation method used in the present invention is 1.00.

[0059] The color of the pigment of the present invention is not particularly limited. However, since it may be used as a substitute for titanium oxide, it is preferably white like titanium oxide.

[0060] In order to impart hydrophobicity, optical properties, etc., the pigments of the present invention may have a coating layer formed of inorganic substances on the surface of the particles. In addition, a coating layer formed of organic substances may also be present. Two or more coating layers may be present, or both an inorganic layer and an organic layer may be included.

[0061] An example of the method for manufacturing the pigment of the present invention is shown. It should be noted that the method for manufacturing the pigment of the present invention is not limited to the following.

[0062] The pigment formed of particles mainly composed of the perovskite composite oxide of the present invention is manufactured by a method called the atmospheric pressure heating reaction method, which includes mixing an acid peptized product of a hydrolyzate of a titanium compound, a water-soluble compound containing calcium, and an alkali under atmospheric pressure, and heating to 70 °C or higher and 100 °C or lower to synthesize the perovskite composite oxide. The acid peptized product of the hydrolyzate of the titanium compound is typically metatitanic acid obtained by a method called the sulfuric acid method. After obtaining the perovskite composite oxide by the above method, decalcification treatment is preferably performed.

[0063] (Sulfuric acid method)

[0064] Dissolve ilmenite with concentrated sulfuric acid, and remove the generated ferric sulfate component, whereby metatitanic acid shown by the chemical formula TiO(OH) 2 can be obtained.

[0065] (Atmospheric pressure heating reaction method)

[0066] As the acid peptized product of the hydrolyzate of the titanium compound, metatitanic acid can be cited. As metatitanic acid, a compound having a sulfur content of 15 g / kg or less, preferably 10 g / kg or less in terms of SO 3 is preferably used as the hydrolyzate of the titanium compound, and the pH of the hydrolyzate is adjusted to 0.8 or higher and 1.5 or lower with hydrochloric acid, and the resulting substance is peptized. Thus, perovskite composite oxide particles with a small particle size distribution can be obtained. When the sulfur in metatitanic acid is more than 15 g / kg in terms of SO 3 conversion, peptization may sometimes not be possible. In addition to hydrochloric acid, nitric acid, hydrogen bromide, hydrogen iodide, formic acid, acetic acid, etc. can also be used. In addition, as an alternative to the acid peptized product of the hydrolyzate of the titanium compound, a substance obtained by neutralizing the peptized product with an alkali can also be used.

[0067] As the alkali mixed with the acid peptized product of the hydrolyzate of the titanium compound, caustic alkali can be used, and sodium hydroxide is preferably used. The concentration of the alkali in the mixture in the above atmospheric pressure heating reaction method is preferably 0.1 mol / L or higher, more preferably in the range of 0.5 mol / L or higher and 3.6 mol / L or lower.

[0068] As factors affecting the crystallinity and particle size of a pigment containing particles mainly composed of a perovskite composite oxide obtained by the aforementioned atmospheric pressure heating reaction method, the concentration and mixing ratio of raw materials, the concentration of alkali, the reaction temperature, additives, etc. can be cited. The mixing ratio of the acid peptized product of the hydrolyzate of a titanium compound and a water-soluble compound containing calcium is preferably such that the amount of substance of calcium (Ca element) is 1.00 times or more and 1.60 times or less with respect to the amount of substance of titanium (Ti element), and more preferably 1.10 times or more and 1.50 times or less. Since the acid peptized product of the hydrolyzate of a titanium compound has low solubility in water, when the amount of substance of calcium is less than that of titanium, in the reaction product, not only perovskite composite oxide particles remain, but unreacted titanium oxide also easily remains. As the concentration of the acid peptized product of the hydrolyzate of a titanium compound in the mixture in the atmospheric pressure heating reaction method, it is preferably 0.5 mol / L or more and 1.5 mol / L or less in terms of Ti, and more preferably 0.7 mol / L or more and 1.4 mol / L or less.

[0069] The higher the temperature during the reaction, the better the crystallinity of the resulting product. However, a reaction at a temperature above 100 °C requires a pressure vessel, so a range of 70 °C or more and 100 °C or less is appropriate in practice, and it can also be a range of 70 °C or more and less than 100 °C.

[0070] When making the particle shape approximately spherical, during the atmospheric pressure heating reaction, as an additive, one or more selected from monosaccharides and disaccharides such as glucose and maltose can be added. When adding sugar as described above, their total concentration is preferably 0.0115 mol / mol or more and 0.0195 mol / mol or less with respect to the amount of calcium added during the atmospheric pressure heating reaction. When the concentration is less than 0.0115 mol / mol, the particles will not become approximately spherical, and when it is greater than 0.0195 mol / mol, there is a tendency for titanium oxide to easily remain. Additionally, generally, when the amount of sugar added is large, there is a tendency for the particles to decrease, but when used in cosmetics, it is preferred that the particles are not too small. From this aspect, the concentration of added sugar is preferably 0.0195 mol / mol or less.

[0071] During the atmospheric pressure heating reaction, one or more compounds selected from aliphatic hydroxy acid compounds such as citric acid and isocitric acid can also be added. When adding an aliphatic hydroxy acid compound, the aspect ratio of the particles increases. The addition amount of the aliphatic hydroxy acid is preferably 0.0180 mol / mol or less with respect to the amount of calcium added during the atmospheric pressure heating reaction.

[0072] (Decalcification treatment)

[0073] After synthesizing the perovskite composite oxide through an atmospheric pressure heating reaction, in order to prevent unreacted calcium from remaining and hindering surface treatment, it is preferable to perform a decalcification treatment. The decalcification treatment includes: adjusting the pH to 2.5 or more and 7.0 or less, more preferably adjusting the pH to 4.5 or more and 6.0 or less, using hydrochloric acid. In addition to hydrochloric acid, nitric acid, acetic acid, etc. can also be used. When the pH is greater than 7.0, the unreacted calcium cannot be completely removed. On the other hand, when the pH is less than 2.5, the calcium in the perovskite composite oxide flows out into the acid, and titanium oxide may be partially formed.

[0074] (Surface covering treatment)

[0075] In the present invention, for a pigment containing particles mainly composed of a perovskite composite oxide, for example, for the purpose of improving the dispersion stability and durability in a dispersion medium when manufacturing cosmetics, at least a part of the particle surface can be covered with an inorganic covering layer such as a metal hydroxide or oxide containing aluminum, silicon, zinc, titanium dioxide, zirconium, iron, cerium, and tin. Metal salts other than the above can also be used as the inorganic covering. In addition, in order to perform surface modification represented by hydrophobic treatment on at least a part of the particle surface of the pigment of the present invention, an organic covering layer can also be covered. Examples of the organic covering include methods of treating organosilicon compounds such as polydimethylsiloxane and methylhydrogenpolysiloxane, coupling agents such as silane-based, aluminum-based, titanium dioxide-based, and zirconium-based, fluorine compounds such as perfluoroalkyl phosphate compounds, hydrocarbons, lecithin, amino acids, polyethylene, wax, metal soaps, etc. Multiple of these treatments can also be combined and implemented, and the order of treatment is not particularly limited in this case.

[0076] (Use of the pigment)

[0077] The pigment of the present invention can selectively transmit light in the warm color region. When used as a material for cosmetics applied to the skin, the light in the warm color region transmitted scatters inside the skin, thereby suppressing powder floating and achieving a natural makeup look. Therefore, the pigment of the present invention can be suitably used as a material for cosmetics. A cosmetic containing the pigment of the present invention is one aspect of the present invention. Additionally, from another perspective, it is also one aspect of the present invention that the pigment containing particles mainly composed of perovskite composite oxide is used in the form of a cosmetic, and it is also one aspect of the present invention that the pigment containing particles mainly composed of perovskite composite oxide is used in cosmetics to suppress the powder floating phenomenon. Here, the "powder floating phenomenon" refers to the phenomenon that when applying cosmetics to the skin, when the intensity of the white scattered light is strong, the makeup look of the colored makeup appears pale and unnatural. "Suppressing the powder floating phenomenon" means that the pigment of the present invention blended in the cosmetics will selectively transmit light in the warm color region, and the light in the warm color region transmitted scatters inside the skin, thereby suppressing, reducing or alleviating the above-mentioned powder floating phenomenon, so that the makeup look of the colored makeup becomes a natural makeup look. It should be noted that the "light in the warm color region" refers to light with a wavelength of 570 nm or more and 780 nm or less.

[0078] In addition, the pigment of the present invention can exhibit the function of transmitting light in the warm color region in fields other than cosmetics and is widely used in various applications. As such applications, for example, but not limited to these, it can be mentioned that it is added to a transparent material and formed into a film for use in components of optical instruments, added to a resin for use in automotive sunroofs, etc., added to a coating for performing a coating that transmits light in the warm color region, etc. In addition, the pigment obtained in the present invention can also be used as a substitute material for titanium oxide.

[0079] (Cosmetics)

[0080] When using the pigment of the present invention as a cosmetic, typically, after performing the above-mentioned covering treatment on the surface, inorganic pigments and / or organic pigments, etc. can be mixed according to a known method. The content of the pigment of the present invention in the cosmetic varies depending on the type of the cosmetic and is not particularly limited. For example, if it is a powder-type cosmetic, it is 1 g / kg or more and 900 g / kg or less; if it is an oil-type cosmetic, it is 1 g / kg or more and 500 g / kg or less; if it is an emulsion-type or paste-type cosmetic, it can be used in an amount of 1 g / kg or more and 150 g / kg or less, but is not limited to this range.

[0081] When using the pigment of the present invention as a cosmetic, as the inorganic pigment and / or organic pigment that can be mixed, the inorganic pigments, organic pigments, etc. used in ordinary cosmetics can be used as needed. Examples of such inorganic pigments include titanium oxide, zinc oxide, iron oxide represented by iron oxide red, cerium oxide, aluminum oxide, zirconium oxide, magnesium oxide, chromium oxide, magnesium silicate, magnesium aluminum silicate, calcium silicate, barium sulfate, magnesium sulfate, calcium sulfate, calcium carbonate, magnesium carbonate, talc, mica, surface-treated mica, mica-like synthetic pigments, sericite, zeolite, kaolin, bentonite, clay, silicic acid, boron nitride, bismuth oxychloride, hydroxyapatite, ultramarine, Prussian blue, and their dehydrates, complexes, etc. Examples of the same organic pigments include silicone powder, silicone elastic powder, polyurethane powder, cellulose powder, nylon powder, urethane powder, silk fibroin powder, polymethyl methacrylate (hereinafter referred to as "PMMA") powder, polyethylene powder, starch, carbon black, metal soaps such as zinc stearate, and their complexes, etc. In addition, tar pigments and various natural pigments can also be used.

[0082] The manufacturing method of the cosmetic is not particularly limited, and known methods can be used. The dosage form of the cosmetic is not particularly limited. For example, it can be in any state such as powdery, powder-solid form, paste, emulsion form, lotion form, oily liquid form, oily solid form, paste form, etc. For example, it can be made into makeup cosmetics such as primer, foundation, concealer, face powder, color corrector, sunscreen cosmetics, lipstick, blush, lip balm, lip gloss, lip honey, eyeshadow, eyeliner, mascara, blush palette, nail polish, body powder, face powder, baby powder, etc., skin care cosmetics, hair care cosmetics, etc. From the viewpoint of maximizing the light transmission effect and lubricity of the warm color region based on the pigment of the present invention, it is preferably used for coated makeup cosmetics applied to the skin.

[0083] It should be noted that in the cosmetics of the present invention, in addition to the above components, other components can be compounded according to the purpose within the range of the amount and quality that do not damage the effects of the present invention. For example, oily components, pigments, pH regulators, moisturizers, thickeners, surfactants, dispersants, stabilizers, colorants, preservatives, antioxidants, metal masking agents, astringents, anti-inflammatory agents, ultraviolet absorbers, fragrances, and some pharmaceuticals can be appropriately compounded according to the purpose.

[0084] In addition to cosmetics, the pigments of the present invention can also be used in fields such as film compositions, resin compositions, coatings, inks, etc. That is, a film composition, resin composition, coating, or ink containing the pigment of the present invention is one aspect of the present invention. Additionally, from another perspective, the use of the pigment of the present invention containing particles mainly composed of perovskite composite oxides in a film composition, resin composition, coating, or ink is also one aspect of the present invention. Further, for example, it can be said that the use of the pigment of the present invention containing particles mainly composed of perovskite composite oxides for manufacturing a film composition, resin composition, coating, or ink that allows good transmission of light in the warm color region is also one aspect of the present invention.

[0085] The pigment of the present invention can be used as one of the materials for a film composition. Specifically, the film composition containing the pigment of the present invention is not limited to these and can be used in optical instruments, solar power generation devices, etc. The film composition is mainly manufactured from resins represented by polyethylene terephthalate, polypropylene, polyvinyl alcohol, fluororesins, etc., glass, porous materials, bio-derived materials, etc. The film composition is manufactured by a known method. For example, a resin is dissolved in a solvent such as an organic solvent or water, mixed with the pigment of the present invention previously dispersed in the solvent, poured into a mold, and dried, thereby obtaining a film composition containing the material of the present invention. A dispersant, other pigments, colorants, antistatic agents, etc. can be optionally used in combination. The pigment of the present invention is not limited to this range and is preferably added in such a manner that it becomes 1 g / kg or more and 250 g / kg or less in the obtained film composition. By using the pigment of the present invention, a film composition that selectively transmits light in the warm color region can be obtained.

[0086] The pigment of the present invention can be used as one of the materials for a resin composition. Specifically, the resin composition containing the pigment of the present invention is not limited to these and can be used in automotive skylights, resin containers, etc. As the resin, any of thermoplastic resins such as polyethylene and polypropylene, and thermosetting resins such as polycarbonate can be used. The resin composition is manufactured by a known method. For example, a monomer and the pigment of the present invention are dispersed in a solvent such as an organic solvent or water, a polymerization initiator is added and heated, and then washed and dried, thereby obtaining a resin composition containing the pigment of the present invention. A flame retardant, filler, etc. can be optionally used in combination. The pigment of the present invention is not limited to this range and is preferably added in such a manner that it becomes 1 g / kg or more and 350 g / kg or less in the obtained resin composition. By using the pigment of the present invention, a resin composition that transmits light in the warm color region, a resin composition with a warm color light and white color can be obtained.

[0087] The pigment of the present invention can be used as one of the materials for coatings. Specifically, the coating containing the pigment of the present invention is not limited thereto and can be used for residential coatings in cold regions, etc. The pigment of the present invention can also be used for water-based coatings and oil-based coatings. The coating can be obtained from resins such as acrylic resin, urethane resin, polyvinyl alcohol, solvents such as toluene, ethanol, water, and colorants represented by the pigment of the present invention. The coating is manufactured by a known method. For example, a curing agent is added to the resin, and further the pigment obtained by the present invention and a solvent are added and stirred, whereby a coating containing the pigment of the present invention is obtained. An anti-settling agent, a preservative, and other pigments can be optionally used in combination. The pigment of the present invention is not limited to this range, and is preferably added in such a manner that it becomes 1 g / kg or more and 700 g / kg or less in the dried coating film after use. By using the pigment of the present invention, a residential coating, etc. that can transmit light in the warm color region well and thus raise the indoor temperature can be obtained.

[0088] The pigment of the present invention can be used for inks. Specifically, the ink containing the pigment of the present invention is not limited to these, and special inks printed on films, glass surfaces, etc. can be used. The ink can be obtained from colorants represented by the pigment obtained by the present invention, resins such as acrylic resin, and solvents such as ketones, hydrocarbons, and water. The ink is manufactured by a known method. For example, the ink is obtained by dispersing and mixing the colorant, resin, and solvent. A pH adjuster, a surfactant, a preservative, and pigments other than the pigment obtained by the present invention can be optionally used in combination. The pigment of the present invention is not limited to this range, and is preferably added in such a manner that it becomes 1 g / kg or more and 600 g / kg or less in the obtained ink. By using the pigment of the present invention, for example, when printed on transparent substrates such as plastics and glass, it can impart aesthetics that current white pigments do not have.

[0089] In addition to the above, the pigment of the present invention can be used for uses such as paper, external additives for toners, coating tools, fiber products, packaging materials, coating films, coating materials, etc.

[0090] Before the description of the examples, the test methods used in the present invention will be described.

[0091] (Lattice constant a)

[0092] Using the Rigaku Corporation X-ray diffractometer RINT-TTR III, X-ray diffraction measurement based on the powder method was carried out. The sample amount was sealed in a cuvette at about 1.5 g ± 0.2 g after being ground in a mortar. The starting angle was set at 5.0000°, the ending angle was set at 90.0000°, the sampling width was set at 0.0100°, the scanning speed was set at 10.0000° / minute, the divergence slit was set at 0.5°, the scattering slit was set at 0.5°, the width of the receiving slit was set at 0.15 mm, the cathode of the characteristic X-ray used copper, and the wavelength was set at 0.15418 nm. For the obtained X-ray diffraction pattern, using the analysis software MDIJADE7 manufactured by Material Data Inc., smoothing, background processing, and peak detection were performed, and the lattice constant a was calculated.

[0093] (XRD Diffraction Line Height Ratio and XRD Titanium Oxide Integral Diffraction Intensity)

[0094] For the X-ray diffraction pattern measured by the above method, using the powder X-ray analysis software PDXL2 manufactured by Rigaku Corporation, background processing, smoothing, and peak detection were carried out. When the height of the highest part of the diffraction line of the largest diffraction line in the range of diffraction angle 2θ of 32.50° or more and 33.50° or less was set to 100.0, the height of the highest part of the largest diffraction line in the range of diffraction angle 2θ of 46.75° or more and 47.75° or less was calculated and used as the XRD diffraction line height ratio. In addition, when the integral diffraction intensity of the largest diffraction line in the range of diffraction angle 2θ of 32.50° or more and 33.50° or less was set to 100.0, the integral diffraction intensity of the largest diffraction line appearing in the range of diffraction angle 2θ of 24.75° or more and 28.00° or less was calculated and used as the XRD titanium oxide integral diffraction intensity.

[0095] (Microcrystalline Diameter)

[0096] The full width at half maximum of the diffraction line of the (121) plane obtained from the X-ray diffraction pattern measured by the above method was introduced into the following Sherrer formula to calculate the microcrystalline diameter D 121 :

[0097] D 121 = kλ / βcosθ

[0098] In the formula, the constant k is 0.9, λ is the wavelength of the X-ray, β is the full width at half maximum of the diffraction line of the (121) plane, and cosθ is the value based on the diffraction angle 2θ at which the diffraction line appears.

[0099] (Specific Surface Area)

[0100] For the specific surface area, it was measured by the BET one-point method using Gemini VII2390 manufactured by MICROMETORITICS.

[0101] (Particle size distribution)

[0102] The particle size distribution was measured by the method based on JIS Z 8825:2013 using a laser diffraction scattering particle size analyzer Microtrac (registered trademark) MT3300EX II manufactured by Microtrac BEL Corp. The dispersion medium used was ion-exchanged water. After appropriately dropping the pigment into the ultrasonic dispersion tank of the automatic sample circulator attached to the measuring device, ultrasonic dispersion was performed at a power of 40 W for 360 seconds. Then, for each measurement parameter, the refractive index of ion-exchanged water was set to 1.33, the light transmittance of the particles to be measured was set to reflection, the measurement time was set to 30 seconds, and the particle diameter (X10) corresponding to 10% of the cumulative particle size distribution (volume basis) and the particle diameter (X90) corresponding to 90% of the cumulative particle size distribution (volume basis) were measured. X90 / X10 was used as an index of the particle size distribution.

[0103] (Roundness and average roundness)

[0104] The roundness was calculated using (4π×S) / L, where S is the area of the particle in the two-dimensional projection of the particle and L is the measured perimeter of the particle. 2 It was obtained by using a transmission electron microscope JEM-1400plus manufactured by JEOL Ltd. to photograph the particles at an observation magnification of 10,000 times and using image analysis software ImageJ to calculate the roundness. In addition, the average roundness was taken as the average of the roundness of 200 particles.

[0105] (Warm-color light transmission effect)

[0106] Using an H3 type automatic grinder manufactured by Toyo Seiki Seisaku-sho, Ltd., 3 mL of styrenated alkyd resin and 0.5 g of pigment were kneaded to form a coating. The obtained dispersion was coated on a black and white hiding power test paper JIS-K5 / 400 using a 3-mm spatula and sintered at 130 °C for 30 minutes to obtain a test sample. The reflectance of the test sample in black at wavelengths above 380 nm and below 780 nm was measured using a spectrophotometric color difference meter SQ-2000 manufactured by Nippon Denshoku Industries Co., Ltd. The transmittance at each wavelength was calculated by subtracting the measured value from 100%. The total transmittance light amount was the sum of the transmittances at wavelengths above 380 nm and below 780 nm, the warm-color transmittance light amount was the sum of the transmittances at wavelengths above 570 nm and below 780 nm, and the value of warm-color transmittance light amount / total transmittance light amount was the warm-color light transmission effect.

[0107] Examples

[0108] Hereinafter, the present invention will be specifically described by way of examples. However, the following examples are merely illustrative and do not limit the scope of the invention.

[0109] It should be noted that in the stirring operations described in the examples and comparative examples, considering the properties related to the state of the liquid during stirring, such as the liquid volume, the viscosity of the liquid, and the shape of the container, the rotation speed was appropriately adjusted so that the entire liquid was uniformly mixed and droplets did not scatter to the surroundings. In addition, when using common commercially available products such as sodium hydroxide that give the same effect regardless of the manufacturer, the company names of the manufacturers and sellers are omitted.

[0110] [Example 1]

[0111] After subjecting the metatitanic acid obtained by the sulfuric acid method to iron removal and bleaching treatment, an aqueous sodium hydroxide solution was added to adjust the pH to 9.0, and desulfurization treatment was carried out. Then, it was neutralized with hydrochloric acid to pH 5.8, followed by filtration and washing with water to obtain a metatitanic acid filter cake with a sulfur content of 9.3 g / kg in terms of SO 3 Conversion. Water was added to the washed filter cake to make a slurry with a Ti concentration of 2.13 mol / L, and then hydrochloric acid was added to adjust the pH to 1.4 for peptization treatment. The slurry after extraction treatment with 2.25 mol of TiO 2 was put into a reaction vessel with a capacity of 3000 mL. Calcium hydroxide was added thereto such that the amount of calcium in terms of Ca became 1.15 times the amount of titanium in terms of Ti, 0.36 mol of sodium hydroxide was added, and water was added to make the total volume 2.0 L. The mixed solution was stirred for 30 minutes using HEIDON600G manufactured by Shinto Kagaku Co., Ltd.

[0112] The above-mentioned slurry was further stirred and mixed, and then heated to 95 °C using a B-E type hooded heater manufactured by Tokyo Institute of Technology Co., Ltd., and continuously stirred for 18 hours to complete the reaction (atmospheric pressure heating reaction). The stirred slurry was naturally cooled to 50 °C, hydrochloric acid was added to adjust the pH to 5.0, and stirring was further continued for 1 hour (decalcification treatment). The obtained precipitate was decanted and washed, separated by filtration, and then dried at 120 °C for 10 hours in the atmosphere using a thermostat PHH-202 manufactured by ESPEC CORP. The dried product was pulverized using an Ishikawa type stirring and crushing machine A-G type (hereinafter referred to as "automatic mortar") manufactured by Ishikawa Works Co., Ltd. to obtain a white pigment. The pigment was evaluated by the above test method, and the results showed that the lattice constant a was The XRD diffraction line height ratio was 37.3, the specific surface area was 12.2 m 2 / g, the integrated diffraction intensity of XRD titanium oxide was 6.07, the particles were cuboid-shaped, the microcrystalline diameter was The particle size distribution was 2.81, and the average circularity was 0.720. In addition, the warm color light transmission effect was 0.64.

[0113] [Example 2]

[0114] After adding calcium hydroxide, the amount of sodium hydroxide added was changed to 1.80 mol. Except for this, the atmospheric pressure heating reaction, decalcification treatment, washing, filtration, drying, and pulverization were carried out under the same conditions as in Example 1 to obtain a white pigment. The lattice constant a of this pigment was The XRD diffraction line height ratio was 38.3, the specific surface area was 6.1 m 2 / g, the XRD titanium oxide integrated diffraction intensity was 5.85, the particles were rectangular parallelepiped-shaped, and the microcrystalline diameter was The particle size distribution was 2.92, and the average circularity was 0.698. In addition, the warm-color light transmission effect was 0.58.

[0115] [Example 3]

[0116] After adding calcium hydroxide, the amount of sodium hydroxide added was changed to 7.20 mol. Except for this, the atmospheric pressure heating reaction, decalcification treatment, washing, filtration, drying, and pulverization were carried out under the same conditions as in Example 1 to obtain a white pigment. The lattice constant a of this pigment was The XRD diffraction line height ratio was 37.8, the specific surface area was 4.4 m 2 / g, the XRD titanium oxide integrated diffraction intensity was 4.24, the particles were rectangular parallelepiped-shaped, and the microcrystalline diameter was The particle size distribution was 4.26, and the average circularity was 0.692. In addition, the warm-color light transmission effect was 0.56.

[0117] [Example 4]

[0118] After adding calcium hydroxide, the amount of sodium hydroxide added was changed to 3.60 mol, and 0.0193 mol of glucose was added relative to 1 mol of Ca after adding sodium hydroxide. Except for this, the atmospheric pressure heating reaction, decalcification treatment, washing, filtration, drying, and pulverization were carried out under the same conditions as in Example 1 to obtain a white pigment. The lattice constant a was The XRD diffraction line height ratio was 33.2, the specific surface area was 27.4 m 2 / g, the XRD titanium oxide integrated diffraction intensity was 3.14, the particles were roughly spherical, and the microcrystalline diameter was The particle size distribution was 2.71, and the average circularity was 0.835. In addition, the warm-color light transmission effect was 0.63.

[0119] [Example 5]

[0120] With respect to 1 mol of Ca, the addition amount of glucose was changed to 0.0077 mol. Except for this, the atmospheric pressure heating reaction, decalcification treatment, washing, filtration, drying, and pulverization were carried out under the same conditions as in Example 4 to obtain a white pigment. The lattice constant a of this pigment was The XRD diffraction line height ratio was 38.0, the specific surface area was 5.5 m 2 / g, the XRD titanium oxide integrated diffraction intensity was 5.31, the particles were cuboid-shaped, and the microcrystalline diameter was The particle size distribution was 3.02, and the average circularity was 0.740. In addition, the warm-color light transmission effect was 0.59.

[0121] [Example 6]

[0122] With respect to 1 mol of Ca, after adding glucose, 0.0166 mol of citric acid was added. Except for this, the atmospheric pressure heating reaction, decalcification treatment, washing, filtration, drying, and pulverization were carried out under the same conditions as in Example 5 to obtain a white pigment. The lattice constant a of this pigment was The XRD diffraction line height ratio was 40.9, the specific surface area was 8.0 m 2 / g, the XRD titanium oxide integrated diffraction intensity was 8.42, the particles were cuboid-shaped, and the microcrystalline diameter was The particle size distribution was 2.67, and the average circularity was 0.614. In addition, the warm-color light transmission effect was 0.58.

[0123] [Example 7]

[0124] With respect to 1 mol of Ca, the addition amount of glucose was changed to 0.0039 mol. Except for this, the atmospheric pressure heating reaction, decalcification treatment, washing, filtration, drying, and pulverization were carried out under the same conditions as in Example 4 to obtain a white pigment. The lattice constant a of this pigment was The XRD diffraction line height ratio was 45.7, the specific surface area was 3.6 m 2 / g, the XRD titanium oxide integrated diffraction intensity was 5.22, the particles were cuboid-shaped, and the microcrystalline diameter was The particle size distribution was 3.51, and the average circularity was 0.699. The warm-color light transmission effect was 0.56.

[0125] [Example 8]

[0126] The extraction amount of the deflocculated slurry was changed to 1.50 mol based on TiO 2 calculation, the addition amount of sodium hydroxide was changed to 0.60 mol, the holding time at 95 °C was changed to 4 hours, the drying temperature after separation based on filtration was changed to 60 °C, and the drying time was changed to 2 hours. Except for this, in the same manner as in Example 1, a white pigment was obtained. The lattice constant a of this pigment was The height ratio of the XRD diffraction line is 41.5, the specific surface area is 9.4 m 2 / g, the integrated diffraction intensity of titanium oxide in XRD is 5.33, the particles are cuboid-shaped, and the microcrystalline diameter is The particle size distribution is 2.44, and the average roundness is 0.689. The transmission effect of warm-color light is 0.59.

[0127] [Example 9]

[0128] After drying the pigment obtained in Example 8, it was calcined in air at 300 °C using SUPER-CC-2035D manufactured by MOTOYAMA CO., LTD. (hereinafter referred to as "calcining furnace") to obtain a white pigment. The lattice constant a of this pigment is The height ratio of the XRD diffraction line is 41.7, the specific surface area is 8.2 m 2 / g, the integrated diffraction intensity of titanium oxide in XRD is 4.85, the particles are cuboid-shaped, and the microcrystalline diameter is The particle size distribution is 2.52, and the average roundness is 0.655. The transmission effect of warm-color light is 0.59.

[0129] [Comparative Example 1]

[0130] A pigment mainly composed of a perovskite composite oxide was synthesized by a conventional calcination method. Specifically, metatitanic acid, which is the peptized product described in Example 1, and calcium carbonate were added in such a way that the molar amount of calcium in terms of Ca was 1.15 times the molar amount of titanium in terms of Ti, and the mixture was rehydrated so that the solid component concentration became 200 g / L. After adjusting the pH to 10.0 with sodium oxide, it was dispersed and mixed using Ultra Apexmill UAM-015 manufactured by Hiroshima Metal & Machinery Co., Ltd. (hereinafter referred to as "bead mill"). After separating the solid component of this slurry by filtration, it was dried in air at 120 °C for 10 hours. The dried product was calcined in air at 1100 °C for 1 hour using a calcining furnace and then pulverized with an automatic mortar to obtain a light pink pigment. The lattice constant a of this pigment is The height ratio of the XRD diffraction line is 54.0, the specific surface area is 4.7 m 2 / g, the integrated diffraction intensity of titanium oxide in XRD is 2.63. Since a part of the particles dissolved and fused with each other during calcination at high temperature, the particles are approximately spherical, and the microcrystalline diameter is The particle size distribution is 19.92, and the average roundness is 0.818. The transmission effect of warm-color light is 0.51.

[0131] [Comparative Example 2]

[0132] The pigment obtained in Example 1 was calcined in a calcination furnace set at 1100 °C for 1 hour, and then pulverized with an automatic mortar to obtain a light earth-yellow pigment. The lattice constant a of this pigment was The XRD diffraction line height ratio was 53.2, the specific surface area was 6.7 m 2 / g, the XRD titanium oxide integrated diffraction intensity was 2.55, the particles were approximately spherical, and the crystallite diameter was The particle size distribution was 63.54, and the average circularity was 0.838. The warm-color light transmission effect was 0.53.

[0133] [Comparative Example 3]

[0134] The pigment obtained in Example 4 was calcined in a calcination furnace set at 1100 °C for 1 hour, and then pulverized with an automatic mortar to obtain a light yellowish-brown pigment. The lattice constant a of this pigment was The XRD diffraction line height ratio was 52.2, the specific surface area was 5.4 m 2 / g, the XRD titanium oxide integrated diffraction intensity was 2.05, the particles were approximately spherical, and the crystallite diameter was The particle size distribution was 100.82, and the average circularity was 0.822. The warm-color light transmission effect was 0.55.

[0135] [Comparative Example 4]

[0136] The perovskite composite oxide reagent CAF04PB manufactured by the High-Purity Chemical Research Institute Co., Ltd. as a commercially available product was used as Comparative Example 4. The appearance of this reagent was light pink, and the lattice constant a was The XRD diffraction line height ratio was 52.3, the specific surface area was 2.5 m 2 / g, the XRD titanium oxide integrated diffraction intensity was 3.72, the particles were approximately spherical, and the crystallite diameter was The particle size distribution was 13.19, and the average circularity was 0.791. The warm-color light transmission effect was 0.53.

[0137] Table 1 shows the manufacturing conditions of the pigments in the examples and comparative examples, and Table 2 shows the characteristics of the pigments obtained in the examples and comparative examples.

[0138] As shown in Table 2, the pigments of Examples 1 to 9 with a lattice constant a of or more and or less were pigments with a warm-color light transmission effect of 0.56 or more and selectively transmitted light in the warm-color region. On the other hand, the warm-color light transmission effect of the pigments of Comparative Examples 1 to 4 with a lattice constant a less than was as small as 0.55 or less.

[0139] As described above, the pigment of the present invention can selectively transmit light in the warm color region. When the pigment of the present invention is used as a raw material for cosmetics, a natural makeup can be achieved.

[0140] [Table 1]

[0141]

[0142] [Table 2]

[0143]

[0144] Next, the powder foundations made from the respective pigments obtained in the use examples and comparative examples were subjected to sensory evaluation by the following method.

[0145] (Sensory evaluation of powder foundation)

[0146] The respective pigments obtained in the examples and comparative examples were subjected to surface treatment with methylhydrogenpolysiloxane and uniformly mixed using a LAB.MIXER LM-110T manufactured by HANIL Electric.Co.,Ltd (hereinafter referred to as "mixer") according to the compounding ratios shown in Table 3. After pulverizing the mixture with a sample mill TASM-1 manufactured by TOKYO ATOMIZER M.F.G.CO.,LTD (hereinafter referred to as "sample mill"), a specified amount was filled into a gold dish and compression molded to produce a powder foundation.

[0147] [Table 3]

[0148]

[0149] On the wrists and cheeks of 10 panelists, especially at positions with dullness, wrinkles, etc., the respective powder foundations obtained were applied until the dullness, wrinkles, etc. became less obvious, and the naturalness of the makeup and lubricity were evaluated.

[0150] (Natural makeup)

[0151] The impression compared visually with the position where the foundation was not used was evaluated according to the following criteria, and the "natural makeup" was determined based on the average score of 10 panelists. The higher this score, the less the foundation will "cake", and the "natural makeup" is achieved. Table 4 shows the results of the sensory evaluation.

[0152] (Evaluation criteria)

[0153] 5 points: It is impossible to distinguish from the unapplied position even when observed at a very close distance.

[0154] 4 points: When observed from a position 1 m away, it is impossible to distinguish from the unapplied position.

[0155] 3 points: When observed from a position 1 m away, there is no sense of incongruity.

[0156] 2 points: Appears white when observed at very close range.

[0157] 1 point: Appears white even at a relatively far position.

[0158] (Judgment criteria)

[0159] 4.0 or more and less than 5.0 points: A 3.0 or more and less than 4.0 points: B 2.0 or more and less than 3.0 points: C 1.0 or more and less than 2.0 points: D.

[0160] (Lubricity)

[0161] Evaluate the touch when applying the foundation with fingers according to the following criteria, and determine the "lubricity" based on the average score of 10 team members. The higher the score, the better the lubricity of the foundation. Table 4 shows the results of the sensory evaluation.

[0162] (Evaluation criteria)

[0163] 5 points: Can be thinly applied smoothly on the skin.

[0164] 4 points: Can be applied smoothly over a large area.

[0165] 3 points: Can be applied without discomfort.

[0166] 2 points: Poor spreadability.

[0167] 1 point: Has a granular touch when applied on the skin.

[0168] (Judgment criteria)

[0169] 4.0 or more and less than 5.0 points: A 3.0 or more and less than 4.0 points: B 2.0 or more and less than 3.0 points: C 1.0 or more and less than 2.0 points: D.

[0170] [Table 4]

[0171]

[0172] The results of the sensory evaluation show that: compared with the foundation formulated with the pigment of the comparative example, the foundation made with the pigment of the present invention has a natural bare - face look, and also has excellent lubricity. Thus, by formulating the pigment of the present invention in cosmetics, cosmetics with a natural bare - face look and excellent lubricity can be provided.

[0173] [Example 10]

[0174] (Manufacture of powder foundation)

[0175] Mix the following Components 1 to 13 and crush them evenly (Process A). Then, mix Components 15 to 17 evenly and add them to the mixed and crushed material obtained in Process A to make it uniform (Process B). Further, add Component 14 and press and mold it using a mold to obtain a powder foundation (Process C).

[0176] When the obtained powder foundation is applied to the skin, there is no powder floating, and the makeup has a natural bare - face feeling. In addition, good lubricity is also confirmed.

[0177]

[0178]

[0179] (Note 1) The surface was treated with AES - 3083 manufactured by Shin - Etsu Chemical Co., Ltd.

[0180] (Note 2) The surface was treated with KF - 9909 manufactured by Shin - Etsu Chemical Co., Ltd.

[0181] (Note 3) KSP - 300 manufactured by Shin - Etsu Chemical Co., Ltd.

[0182] (Note 4) KMP - 590 manufactured by Shin - Etsu Chemical Co., Ltd.

[0183] (Note 5) KSG - 16 manufactured by Shin - Etsu Chemical Co., Ltd.

[0184] [Example 11]

[0185] (Manufacture of pressed powder)

[0186] Mix and crush the following Components 1 to 7 (Process A). Then, transfer the mixed and crushed material to a mixer, add Components 8 to 12, and stir - mix them in a uniform manner (Process B). Then, crush it using a sample mill and press - mold it in an aluminum tray to obtain a pressed powder (Process C). When the obtained pressed powder is applied to the skin, there is no powder floating, and the makeup has a natural bare - face feeling. In addition, good lubricity is also confirmed.

[0187]

[0188]

[0189] (Note 1) Matsumotomicrosphere M - 100, 7μm product manufactured by Matsumoto Yushi - Seiyaku Co., Ltd. (Note 2) SUNLOVELY C manufactured by Toukai Chemical Industry Co., Ltd.

[0190] [Example 12]

[0191] (Manufacture of loose powder)

[0192] After mixing and pulverizing the following Components 1 to 7 (Step A), the mixture is transferred to a mixer, Components 8 to 10 are added, and the mixture is stirred and mixed in a uniform manner (Step B). Further, the mixture obtained in Step B is pulverized with a sample mill and filled to obtain loose powder (Step C).

[0193] When the obtained loose powder is applied to the skin, there is no floating powder, and the makeup has a natural bare face feeling. In addition, good lubricity was also confirmed.

[0194]

[0195]

[0196] (Note 1) Matsumotomicrosphere S-100, 10 μm product manufactured by Matsumoto Yushi Seiyaku Co., Ltd.

[0197] [Example 13]

[0198] (Manufacture of oil-based foundation)

[0199] The following Components 1 to 6 are mixed with a mixer, pulverized uniformly (Step A), Components 7 to 16 are heated to 85 °C for dissolution, the mixture obtained in Step A is added, and the mixture is stirred uniformly (Step B), defoamed, and then the solid components are added to a tray and slowly cooled to room temperature to obtain an oil-based foundation (Step C).

[0200] When the obtained oil-based foundation is applied to the skin, there is no floating powder, and the makeup has a natural bare face feeling. In addition, good lubricity was also confirmed.

[0201]

[0202]

[0203] (Note 1) The surface was treated with KF-96A-50cs manufactured by Shin-Etsu Chemical Co., Ltd.

[0204] [Example 14]

[0205] (Manufacture of foundation stick)

[0206] Mix the following Components 12 to 16 using a mixer (Step A). Separately, weigh Components 1 to 11 in a container capable of holding the total amount, heat to 85°C, and dissolve them (Step B). Further, weigh Components 17 to 21 in another container and dissolve them (Step C). Then, add the mixture obtained in Step A to the heated and dissolved material obtained in Step B, disperse it uniformly by visual inspection using a stirrer, and further add the heated and dissolved material obtained in Step C and emulsify it (Step D). After defoaming, inject the solid components into a mold and slowly cool to room temperature to obtain a foundation stick (Step E).

[0207] It was confirmed that the obtained foundation stick did not cake when applied to the skin, the makeup had a natural bare face look, and the lubricity was also good.

[0208]

[0209]

[0210] (Note 1) The surface was treated with KF-99P manufactured by Shin-Etsu Chemical Co., Ltd.

[0211] [Example 15]

[0212] (Manufacture of W / O Emulsion Foundation)

[0213] After stirring and mixing the following Components 12 to 14 using a mixer (Step A), add Components 1 to 11 and disperse them uniformly by visual inspection using a stirrer (Step B). On the other hand, heat and dissolve Components 15 to 19 in another container (Step C). Then, add the heated and dissolved material obtained in Step C to the dispersion obtained in Step B, emulsify it, and cool to room temperature to obtain a W / O emulsion foundation (Step D).

[0214] The obtained W / O emulsion foundation did not cake when applied to the skin, the makeup had a natural bare face look, and it was also confirmed that the lubricity was good.

[0215]

[0216]

[0217] (Note 1) Product with an HLB value of 4.5

[0218] (Note 2) RHEOPEARL (registered trademark) ISK manufactured by Chiba Powder Co., Ltd.

[0219] (Note 3) The surface was treated with KF-9901 manufactured by Shin-Etsu Chemical Co., Ltd.

[0220] [Example 16]

[0221] (Manufacture of O / W Emulsion Foundation)

[0222] Heat and dissolve the following Components 1 to 7 at 85°C (Step A). Additionally, mix and pulverize Components 8 to 10 (Step B). Further, heat Components 11 to 15 to 85°C, dissolve and mix them (Step C). After that, add the mixture obtained from Step B to the heat-dissolved product obtained from Step A, disperse it uniformly visually using a stirrer, slowly add it to the dissolved mixture obtained from Step C and emulsify, then stir and cool to room temperature. Then, fill it into an appropriate container to obtain an O / W emulsion foundation (Step D).

[0223] When the obtained O / W emulsion foundation is applied to the skin, it does not cake, the makeup has a natural bare-skin feeling, and in addition, good lubricity is also confirmed.

[0224]

[0225]

[0226] [Example 17]

[0227] (Manufacture of W / O Liquid Foundation)

[0228] After uniformly mixing the following Components 8 to 12 (Step A), mix a part of Component 4 and Component 13, add them to the mixture obtained from Step A, and disperse it uniformly visually using a stirrer (Step B). Additionally, mix Components 1 to 3, the remaining amount of Component 4, and Components 5 to 7, and disperse it uniformly visually using a stirrer (Step C). Further, mix Components 14 to 18 and Component 20, and disperse it uniformly visually using a stirrer (Step D). With stirring, slowly add the mixture obtained from Step D to the mixture obtained from Step C and emulsify, and then add the dispersion obtained from Step B and Component 19 to obtain a W / O liquid foundation (Step E).

[0229] When the obtained W / O liquid foundation is applied to the skin, it does not cake, the makeup has a natural bare-skin feeling, and in addition, good lubricity is also confirmed.

[0230]

[0231]

[0232] (Note 1) KSG-210 manufactured by Shin-Etsu Chemical Co., Ltd.

[0233] (Note 2) KSG-15 manufactured by Shin-Etsu Chemical Co., Ltd.

[0234] (Note 3) KF-6028P manufactured by Shin-Etsu Chemical Co., Ltd.

[0235] (Note 4) 6 mm 2 / second (25 °C) product

[0236] (Note 5) The surface was treated with KF-9909 manufactured by Shin-Etsu Chemical Co., Ltd.

[0237] (Note 6) KP-575 manufactured by Shin-Etsu Chemical Co., Ltd.

[0238] (Note 7) 20 g / kg aqueous solution.

[0239] [Example 18]

[0240] (Manufacture of sunscreen)

[0241] To confirm the UV shielding ability of the pigment of the present invention, a sunscreen was prepared. Component 7 was added to a part of Component 5 below and made uniform, Component 8 and Component 9 were added, and dispersed with a bead mill (Step A). Further, Component 1 to Component 4, the remainder of Component 5, and Component 6 were uniformly mixed (Step B). Furthermore, Component 10 to Component 12 and Component 14 were dispersed uniformly with a stirrer (Step C). Then, the mixture obtained in Step C was added to the mixture obtained in Step B and emulsified, and the dispersion obtained in Step A and Component 13 were added to obtain a sunscreen (Step D).

[0242] It was confirmed that the obtained sunscreen has high UV shielding ability, and there is no powder floating when applied to the skin, and the makeup has a natural bare face feeling; in addition, there is no granular feeling on the skin when applied to the skin, and the lubricity is also good.

[0243]

[0244] (Note 1) KSG-240 manufactured by Shin-Etsu Chemical Co., Ltd.

[0245] (Note 2) KSG-15 manufactured by Shin-Etsu Chemical Co., Ltd.

[0246] (Note 3) KF-6038 manufactured by Shin-Etsu Chemical Co., Ltd.

[0247] (Note 4) KP-575 manufactured by Shin-Etsu Chemical Co., Ltd.

[0248] (Note 5) The surface was treated with AES-3083 manufactured by Shin-Etsu Chemical Co., Ltd.

[0249] [Example 19]

[0250] (Manufacture of film composition)

[0251] A film composition containing the pigment of the present invention is prepared. A part of Component 3 is added to Component 1 and dispersed using a bead mill (Process A). Component 2 and the remaining amount of Component 3 are mixed and heated, and stirred at 95 °C for 10 minutes (Process B). The dispersion obtained in Process A is added, stirred for 5 minutes, then heating is terminated, and it is poured into a mold (Process C). It is dried to obtain a film composition (Process D).

[0252] When the obtained film composition is placed under sunlight, the proportion of transmitted light in the warm color region increases significantly, confirming that it has a warm color light transmission effect.

[0253]

[0254] (Note 1) Polyvinyl alcohol 500 manufactured by Kishida Chemical Co., Ltd.

[0255] [Example 20]

[0256] (Manufacture of resin composition)

[0257] A resin composition containing the pigment of the present invention is prepared. Component 1 is distilled, and then nitrogen is bubbled through it for 30 minutes (Process A). Components 5 and 6 are mixed and dispersed using a bead mill (Process B). The liquid obtained in Process A, Components 2 to 4 are added to Component 7, and while stirring, it is heated. When it reaches 65 °C and after 5 minutes, the dispersion obtained in Process B is added, and stirring is continued while maintaining 65 °C (Process C). After 10 hours, Component 8 is added for neutralization (Process D), filtered, and washed to obtain a resin composition (Process E).

[0258] When the obtained resin composition is placed under sunlight, it is confirmed that the proportion of transmitted light in the warm color region increases significantly, having a warm color light transmission effect.

[0259]

[0260]

[0261] [Example 21]

[0262] (Manufacture of coating)

[0263] A coating containing the pigment of the present invention is prepared. Components 1 to 4 are mixed using a mixer for 30 minutes or more and 120 minutes or less (Process A), and then dispersed using a bead mill (Process B).

[0264] When the obtained coating is applied to a transparent glass substrate and placed under light, it is confirmed that the proportion of transmitted light in the warm color region increases significantly, having a warm color light transmission effect.

[0265]

[0266] [Example 22]

[0267] (Manufacture of Ink)

[0268] Manufacture ink containing the pigment of the present invention. After mixing Components 1 to 4 for 30 minutes or more and 120 minutes or less with a mixer (Process A), disperse for 24 hours with a bead mill (Process B).

[0269] When the obtained coating is applied on a transparent glass substrate and placed under light, it is confirmed that the proportion of transmitted light in the warm color region increases significantly, and it has a warm color light transmission effect.

[0270]

[0271] (Note 1) HOMOGENOL (registered trademark) L-18 manufactured by Kao Corporation

[0272] (Note 2) Orgonite (registered trademark)-T manufactured by Nippon Organo Clay Co., Ltd.

Claims

1. A pigment having a lattice constant a of or more and or less, and containing particles mainly composed of a perovskite composite oxide, where the meaning of the main component is that 850 g / kg or more of each particle constituting the pigment is a particle of a perovskite composite oxide. The specific surface area of the pigment is 3.0 m 2 / g or more and 200 m 2 / g or less, In X-ray diffraction measurement, when the height of the diffraction line of the (121) plane appearing in the range of diffraction angle of 32.50° or more and 33.50° or less is set to 100.0, the height of the diffraction line of the (202) plane appearing in the range of diffraction angle of 46.75° or more and 47.75° or less is 50.0 or less.

2. The pigment according to claim 1, wherein, the perovskite composite oxide is an orthorhombic perovskite composite oxide.

3. The pigment according to claim 1 or 2, wherein, in X-ray diffraction measurement, when the integrated diffraction intensity of the (121) plane appearing in the range of diffraction angle of 32.50° or more and 33.50° or less is set to 100.0, in the range of diffraction angle of 24.75° or more and 28.00° or less, there is no diffraction line with an integrated diffraction intensity greater than 12.

00.

4. The pigment according to claim 1 or 2, wherein, at least a part of the surface of the particles has a covering layer of inorganic substances and / or organic substances.

5. The pigment according to claim 1 or 2, wherein, the particle shape is substantially spherical.

6. The pigment according to claim 1 or 2, wherein, the particle shape is rectangular parallelepiped.

7. The pigment according to claim 1 or 2, wherein, The microcrystalline diameter of the particles is or more and or less.

8. A cosmetic comprising the pigment according to any one of claims 1 to 7.

9. A film composition comprising the pigment according to any one of claims 1 to 7.

10. A resin composition comprising the pigment according to any one of claims 1 to 7.

11. A coating comprising the pigment according to any one of claims 1 to 7.

12. An ink comprising the pigment according to any one of claims 1 to 7.

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